2,3,5,6-Tetrafluorophenol → (S)-3-Benzyloxycarbonylamino-4-oxo-5-(2,3,5,6-tetrafluoro-phenoxy)-pentanoic Acid Tert-Butyl Ester

HRID 655823

反応式

HRID 655823 の反応式
[F-].[K+].[C:3]([O:7][C:8](=[O:26])[CH2:9][C@H:10]([NH:15][C:16]([O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)=[O:17])[C:11](=[O:14])[CH2:12]Br)([CH3:6])([CH3:5])[CH3:4].[F:27][C:28]1[C:33]([F:34])=[CH:32][C:31]([F:35])=[C:30]([F:36])[C:29]=1[OH:37]>CN(C=O)C>[C:3]([O:7][C:8](=[O:26])[CH2:9][C@H:10]([NH:15][C:16]([O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)=[O:17])[C:11](=[O:14])[CH2:12][O:37][C:29]1[C:30]([F:36])=[C:31]([F:35])[CH:32]=[C:33]([F:34])[C:28]=1[F:27])([CH3:6])([CH3:5])[CH3:4]

参加物

5

反応物 3

HCID 698582,3,5,6-TetrafluorophenolHCID 522689Potassium FluorideHCID 7020820Z-Asp(OtBu)-bromomethylketone

生成物 1

HCID 57725369(S)-3-Benzyloxycarbonylamino-4-oxo-5-(2,3,5,6-tetrafluoro-phenoxy)-pentanoic Acid Tert-Butyl Ester収率 96%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

Potassium fluoride (2.8 g), was added portionwise to a stirred solution of (S)-3-benzyloxycarbonylamino-5-bromo-4-oxo-pentanoic acid tert-butyl ester (18.6 g) and 2,3,5,6-tetrafluorophenol (9.3 g) in anhydrous DMF (250 mL) under nitrogen at room temperature. The mixture was then stirred for 18 hours before being quenched with ethyl acetate and water. The organic layer was removed and washed with sodium bicarbonate solution, dried (magnesium sulfate) and concentrated to give the sub-title product as an off-white solid (21.1 g, 96%); 1H NMR (400 MHz, CDCl3) δ 1.43 (9H, s), 2.76 (1H, dd), 3.06 (1H, dd), 4.67-4.71 (1H, m), 5.12 (1h, d), 5.22 (1H, d), 5.86 (1H, d), 7.35-7.38 (5H, m); 19F NMR (376 MHz, CDCl3) (proton decoupled) δ −139.98, −140.00, −140.04, −140.06, −157.05, −157.07, −157.11, −157.13; MS ES (+) 486.23 (M+H).

後処理

  1. custombefore being quenched with ethyl acetate and water
  2. customThe organic layer was removed
  3. washwashed with sodium bicarbonate solution
  4. dry with materialdried (magnesium sulfate)
  5. concentrationconcentrated

出典と根拠

ORDレコード
ord-016b11f621fd400d965019e63df854f8
出典データセット
uspto-grants-2011_12
特許番号
US08071618B2

関連ノート

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